US11085422B2 - Coiled and twisted nanofiber yarns for electrochemically harvesting electrical energy from mechanical deformation - Google Patents

Coiled and twisted nanofiber yarns for electrochemically harvesting electrical energy from mechanical deformation Download PDF

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US11085422B2
US11085422B2 US16/624,115 US201816624115A US11085422B2 US 11085422 B2 US11085422 B2 US 11085422B2 US 201816624115 A US201816624115 A US 201816624115A US 11085422 B2 US11085422 B2 US 11085422B2
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yarn
electrode
energy
twisted
harvester
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US20200208614A1 (en
Inventor
Ray H. Baughman
Shaoli Fang
Carter S. Haines
Na Li
Jiangtao Di
Seon Jeong Kim
Shi Hyeong Kim
Keon Jung Kim
Tae Jin Mun
Changsoon Choi
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Industry University Cooperation Foundation IUCF HYU
University of Texas System
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Industry University Cooperation Foundation IUCF HYU
University of Texas System
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Assigned to BOARD OF REGENTS, THE UNIVERSITY OF TEXAS SYSTEM reassignment BOARD OF REGENTS, THE UNIVERSITY OF TEXAS SYSTEM ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DI, JIANGTAO, BAUGHMAN, RAY H., FANG, SHAOLI, HAINES, CARTER S., LI, NA
Assigned to HANYANG UNIVERSITY, SYSTEM AND INDUSTRY-UNIVERSITY COOPERATION FOUNDATION reassignment HANYANG UNIVERSITY, SYSTEM AND INDUSTRY-UNIVERSITY COOPERATION FOUNDATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: Choi, Changsoon, KIM, KEON JUNG, KIM, SEON JEONG, KIM, Shi Hyeong, MUN, TAE JIN
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03G—SPRING, WEIGHT, INERTIA OR LIKE MOTORS; MECHANICAL-POWER PRODUCING DEVICES OR MECHANISMS, NOT OTHERWISE PROVIDED FOR OR USING ENERGY SOURCES NOT OTHERWISE PROVIDED FOR
    • F03G7/00—Mechanical-power-producing mechanisms, not otherwise provided for or using energy sources not otherwise provided for
    • F03G7/008—Mechanical-power-producing mechanisms, not otherwise provided for or using energy sources not otherwise provided for characterised by the actuating element
    • F03G7/012—Electro-chemical actuators
    • F03G7/0121—Electroactive polymers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03G—SPRING, WEIGHT, INERTIA OR LIKE MOTORS; MECHANICAL-POWER PRODUCING DEVICES OR MECHANISMS, NOT OTHERWISE PROVIDED FOR OR USING ENERGY SOURCES NOT OTHERWISE PROVIDED FOR
    • F03G7/00—Mechanical-power-producing mechanisms, not otherwise provided for or using energy sources not otherwise provided for
    • F03G7/008—Mechanical-power-producing mechanisms, not otherwise provided for or using energy sources not otherwise provided for characterised by the actuating element
    • F03G7/009—Actuators with elements stretchable when contacted with liquid rich in ions, with UV light or with a salt solution
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03G—SPRING, WEIGHT, INERTIA OR LIKE MOTORS; MECHANICAL-POWER PRODUCING DEVICES OR MECHANISMS, NOT OTHERWISE PROVIDED FOR OR USING ENERGY SOURCES NOT OTHERWISE PROVIDED FOR
    • F03G1/00—Spring motors
    • F03G1/06—Other parts or details
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03G—SPRING, WEIGHT, INERTIA OR LIKE MOTORS; MECHANICAL-POWER PRODUCING DEVICES OR MECHANISMS, NOT OTHERWISE PROVIDED FOR OR USING ENERGY SOURCES NOT OTHERWISE PROVIDED FOR
    • F03G7/00—Mechanical-power-producing mechanisms, not otherwise provided for or using energy sources not otherwise provided for
    • F03G7/005—Electro-chemical actuators; Actuators having a material for absorbing or desorbing gas, e.g. a metal hydride; Actuators using the difference in osmotic pressure between fluids; Actuators with elements stretchable when contacted with liquid rich in ions, with UV light, with a salt solution
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/38—Threads in which fibres, filaments, or yarns are wound with other yarns or filaments, e.g. wrap yarns, i.e. strands of filaments or staple fibres are wrapped by a helically wound binder yarn
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/441—Yarns or threads with antistatic, conductive or radiation-shielding properties
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03B—MACHINES OR ENGINES FOR LIQUIDS
    • F03B13/00—Adaptations of machines or engines for special use; Combinations of machines or engines with driving or driven apparatus; Power stations or aggregates
    • F03B13/12—Adaptations of machines or engines for special use; Combinations of machines or engines with driving or driven apparatus; Power stations or aggregates characterised by using wave or tide energy
    • F03B13/14—Adaptations of machines or engines for special use; Combinations of machines or engines with driving or driven apparatus; Power stations or aggregates characterised by using wave or tide energy using wave energy
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03G—SPRING, WEIGHT, INERTIA OR LIKE MOTORS; MECHANICAL-POWER PRODUCING DEVICES OR MECHANISMS, NOT OTHERWISE PROVIDED FOR OR USING ENERGY SOURCES NOT OTHERWISE PROVIDED FOR
    • F03G1/00—Spring motors
    • F03G1/02—Spring motors characterised by shape or material of spring, e.g. helical, spiral, coil
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03G—SPRING, WEIGHT, INERTIA OR LIKE MOTORS; MECHANICAL-POWER PRODUCING DEVICES OR MECHANISMS, NOT OTHERWISE PROVIDED FOR OR USING ENERGY SOURCES NOT OTHERWISE PROVIDED FOR
    • F03G1/00—Spring motors
    • F03G1/02—Spring motors characterised by shape or material of spring, e.g. helical, spiral, coil
    • F03G1/026—Spring motors characterised by shape or material of spring, e.g. helical, spiral, coil using torsion springs
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03G—SPRING, WEIGHT, INERTIA OR LIKE MOTORS; MECHANICAL-POWER PRODUCING DEVICES OR MECHANISMS, NOT OTHERWISE PROVIDED FOR OR USING ENERGY SOURCES NOT OTHERWISE PROVIDED FOR
    • F03G5/00—Devices for producing mechanical power from muscle energy
    • F03G5/06—Devices for producing mechanical power from muscle energy other than of endless-walk type
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03G—SPRING, WEIGHT, INERTIA OR LIKE MOTORS; MECHANICAL-POWER PRODUCING DEVICES OR MECHANISMS, NOT OTHERWISE PROVIDED FOR OR USING ENERGY SOURCES NOT OTHERWISE PROVIDED FOR
    • F03G7/00—Mechanical-power-producing mechanisms, not otherwise provided for or using energy sources not otherwise provided for
    • F03G7/08—Mechanical-power-producing mechanisms, not otherwise provided for or using energy sources not otherwise provided for recovering energy derived from swinging, rolling, pitching or like movements, e.g. from the vibrations of a machine
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/10—Inorganic fibres based on non-oxides other than metals
    • D10B2101/12—Carbon; Pitch
    • D10B2101/122—Nanocarbons
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05B—INDEXING SCHEME RELATING TO WIND, SPRING, WEIGHT, INERTIA OR LIKE MOTORS, TO MACHINES OR ENGINES FOR LIQUIDS COVERED BY SUBCLASSES F03B, F03D AND F03G
    • F05B2280/00—Materials; Properties thereof
    • F05B2280/60—Properties or characteristics given to material by treatment or manufacturing
    • F05B2280/6013—Fibres
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/30—Energy from the sea, e.g. using wave energy or salinity gradient

Definitions

  • Yarn energy harvesters containing conducting nanomaterials which yarn energy harvesters that can electrochemically convert the energy change of tensile or torsional deformations directly into electrical energy.
  • Electromagnetic electric energy generators which are basically motors operated in reverse, have been available for almost two centuries, and successfully meet many needs. However, they suffer from low power densities and high cost per Watt when scaled to the millimeter and smaller dimensions needed for emerging applications (Beeby 2009). Piezoelectric and ferroelectric harvesters work well for high-frequency, low-strain deformations (Persano 2013), especially, when individual nanofibers are driven at ultrahigh resonant frequencies (Wang 2006), but lack the elasticity needed for harvesting the energy of large tensile strains. Electrostatic harvesters based on triboelectric charge (Niu 2015; Wen 2014) provide remarkable performance, and are promising for future applications.
  • Rubber-based dielectric capacitors provide an especially attractive way to convert large-stroke mechanical energy into electrical energy.
  • a thin elastomeric sheet is sandwiched between two deformable electrodes (Pelrine 2008; Chiba 2008).
  • An applied voltage (V) typically about a thousand volts, is used to inject a charge, Q, into this elastomeric capacitor.
  • V applied voltage
  • Q charge
  • C capacitance
  • Yarn energy harvesters containing conducing nanomaterials such as carbon nanotube (CNT) yarn energy harvesters
  • CNT carbon nanotube
  • Stretching coiled yarns can generate up to at least 250 W/kg of peak electrical power when cycled up to 24 Hz and can provide up to at least 41.2 J/kg of electrical energy per mechanical cycle.
  • torsional rotation can produce both tensile and torsional energy harvesting and no bias voltage is required, even when electrochemically operating in salt water.
  • the harvesters of invention embodiments are called “twistron harvesters.” Since homochiral and heterochiral coiled harvester yarns provide oppositely directed potential changes when stretched, both can contribute to output power in a dual-electrode yarn. These energy harvesters are used in the ocean to harvest wave energy, combined with thermally-driven artificial muscles to convert temperature fluctuations to electrical energy, sewn into textiles for use as self-powered respiration sensors, and used to power a LED and to charge a storage capacitor.
  • piezoelectrochemical spectroscopy and insights into the hierarchical origins of capacitance have increased fundamental understanding.
  • Inventors have developed CNT yarns that can be stretched to generate a peak electrical power of over 250 W per kg of yarn, without needing an external power source to provide a bias voltage.
  • the invention features a mechanical energy harvester.
  • the mechanical energy harvester includes a first electrode, a second electrode, and an electrolyte. Both the first electrode and the second electrode are immersed in the electrolyte. There exists a path for ionic conductivity between the first electrode and the second electrode.
  • the energy harvester is operable to generate power without an external bias voltage.
  • At least one electrode comprises a twisted, high-electrochemical-surface-area, conductive yarn.
  • Implementations of the invention can include one or more of the following features:
  • the twisted yarn can be additionally coiled.
  • the coil spring index can be between 0.2 and 0.8.
  • the energy harvester can be operable to convert tensile deformation directly into electrical energy.
  • the energy harvester can be operable to convert torsional deformation directly into electrical energy.
  • the energy harvester can include high-surface-area carbon materials.
  • the high-surface-area carbon materials can be selected from a group consisting of carbon nanotubes, carbon nanohorns, graphene, fullerene, activated carbon, carbon black, carbon nanofibers, and combinations thereof.
  • the energy harvester can be operable to provide at least 20 W of peak electrical power per kilogram of the twisted, high-electrochemical-surface-area, conductive yarn when stretched at rates above 20 Hz.
  • the energy harvester can be operable to provide at least 10 J of electrical energy per kilogram of the twisted, high-electrochemical-surface-area, conductive yarn per mechanical cycle.
  • the twisted yarn can be selected from a group consisting of cone spun yarns, funnel spun yarns, Fermat spun yarns, and dual-Archimedean spun yarns.
  • the twisted yarn can have a diameter between 10 ⁇ m and 500 ⁇ m.
  • the twisted yarn can include a twisted single-ply yarn having a diameter between 100 nm and 10 ⁇ m.
  • At least one electrode can include an overcoat that includes an elastomeric barrier material.
  • the elastomeric barrier material can include polyurethane.
  • the electrolyte can include NaCl.
  • the electrolyte can include hydrochloric acid.
  • the electrolyte can be a gel electrolyte.
  • the energy harvester can be operable to generate a change of voltage of at least 50 mV during stretch.
  • the twisted yarn can be wrapped around an elastomeric support.
  • the twisted yarn wrapped around an elastomeric support can be wrapped in a helical manner to provide a homochiral coil.
  • the twisted yarn wrapped around an elastomeric support can be wrapped in a helical manner to provide a heterochiral coil.
  • the harvester can include a plurality of segments which are electrically connected in series, in parallel, or in combinations thereof.
  • Both the first electrode and the second electrode can include twisted, high-electrochemical-surface area, conductive yarn.
  • the first electrode can increase in potential when stretched.
  • the second electrode can decrease in potential when stretched.
  • the first electrode can include homochiral coils.
  • the second electrode can include heterochiral coils.
  • the first electrode and the second electrode can both be homochiral or heterochiral and mechanically deformed with opposite phases.
  • the first energy harvesting electrode and the second energy harvesting electrode can include twisted yarns wrapped around a stretchable core.
  • At least one energy harvesting electrode can include an auxiliary conductor which lowers the impedance of the energy harvester.
  • the first electrode and second electrode can be components of the same yarn.
  • the invention features a textile that includes an above-described energy harvester.
  • the invention features a method of making an energy harvester.
  • the method includes the step of spinning sheets of aligned carbon nanotubes into high strength carbon nanotube yarns.
  • the method further includes the step of inserting twist into the high strength carbon nanotube yarns that are under tension to yield a twisted yarn.
  • the method further includes the step of forming an electrode comprising the twisted carbon nanotube yarn.
  • the method further includes the step of immersing the electrode in an electrolyte.
  • Implementations of the invention can include one or more of the following features:
  • the method can further include a step of inserting additional twist until coils spontaneously form.
  • the method can further include a step of adding a high-surface-area carbon material to the twisted carbon nanotube yarn electrode.
  • the high-surface-area carbon material can be selected from a group consisting of carbon nanotubes, carbon nanohorns, graphene, fullerene, activated carbon, carbon black, carbon nanofibers, and combinations thereof.
  • the electrode can be operable to generate an average electrical power of at least 10 W per kilogram of the carbon nanotube yarn, without requiring an external bias voltage.
  • Tensile or torsional oscillations of the twisted carbon nanotube yarn can be converted directly into electrical energy.
  • the energy harvester can be operable to provide at least 20 W of peak electrical power per kilogram of the carbon nanotube yarn when cycled at rates above 20 Hz.
  • the energy harvester can be operable to provide at least 10 J of electrical energy per kilogram of the carbon nanotube yarn per mechanical cycle.
  • the step of spinning can be selected from a group consisting of cone spinning, funnel spinning, Fermat spinning, tow-spinning, and dual-Archimedean spinning.
  • the step of spinning can be cone spinning.
  • the twisted carbon nanotube yarn can have a diameter between 10 ⁇ m and 500 ⁇ m.
  • the twisted carbon nanotube yarn can have a diameter between 100 nm and 10 ⁇ m.
  • the electrode can include an overcoat comprising an elastomeric barrier material.
  • the elastomeric barrier material can include polyurethane.
  • the electrolyte can include NaCl.
  • the electrolyte can include hydrochloric acid.
  • the invention features a method that includes selecting a twistron mechanical energy harvester that includes an electrode including a twisted, high-electrochemical-surface-area, conductive yarn.
  • the electrode is immersed in an electrolyte.
  • the method further includes applying mechanical energy to deform the yarn by tension, torsion, or combinations thereof, to convert the mechanical energy directly to electrical energy.
  • Implementations of the invention can include one or more of the following features:
  • the minimum applied strain can be selected to prevent yarn snarling from occurring.
  • the twisted, high-electrochemical-surface-area, conductive yarn can be additionally coiled.
  • the yarn can include high-surface-area carbon material.
  • the high-surface-area carbon material can be selected from a group consisting of carbon nanotubes, carbon nanohorns, graphene, fullerene, activated carbon, carbon black, carbon nanofibers, and combinations thereof.
  • the electrode can generate an average electrical power of at least 1 W per kilogram of the twisted, high-electrochemical-surface-area, conductive yarn, without requiring an external bias voltage.
  • the twistron mechanical energy harvester can provide at least 20 W of peak electrical power per kilogram of the twisted, high-electrochemical-surface-area, conductive yarn when stretched at rates above 20 Hz.
  • the twistron mechanical energy harvester can provide at least 1 J of electrical energy per kilogram of the twisted, high-electrochemical-surface-area, conductive yarn, per mechanical cycle.
  • the twisted yarn is selected from a group consisting of cone spun yarns, funnel spun yarns, Fermat spun yarns, and dual-Archimedean spun yarns.
  • the twisted yarn can be a cone spun yarn.
  • the twisted single yarn can have a diameter between 10 ⁇ m and 500 ⁇ m.
  • the twisted single yarn can have a diameter between 100 nm and 10 ⁇ m.
  • the electrode can include an overcoat that includes an elastomeric barrier material.
  • the elastomeric barrier material can include polyurethane.
  • the electrolyte can include NaCl.
  • the twisted yarn can be wrapped around a stretchable core.
  • the twist direction and wrapping direction can be of the same chirality.
  • the twist direction and the wrapping direction can be of opposite chirality.
  • the electrolyte can include hydrochloric acid.
  • the mechanical energy can be supplied by a human body.
  • the mechanical energy can be supplied by an oscillating source.
  • the oscillating source can be ocean waves.
  • the oscillating source can include one or more water wheels.
  • the method can further include utilizing the generated electrical energy to power a device selected from a group consisting of sensor nodes, sensors, actuators, transmitters, wearable electronics, and combinations thereof.
  • the energy harvester can be incorporated into a textile.
  • the invention features an electrochemical mechanical energy harvester that includes an electrolyte-containing electronically conducting yarn electrode that is operable to cause a reversible change in electrochemical capacitance when the level of inserted twist is changed, thereby enabling the harvesting of torsional mechanical energy as electrical energy.
  • the electrochemical mechanical energy harvester further includes a counter electrode.
  • the electrochemical mechanical energy harvester further includes an electrolyte that ionically connects said electronically conducting electrode and said counter electrode.
  • Implementations of the invention can include one or more of the following features:
  • the electrochemical mechanical energy harvester can be operable to cause a reversible change in open circuit voltage of at least 20 mV when the level of inserted twist is changed.
  • the electronically conducting yarn electrode can be operable to cause the reversible change in electrochemical capacitance of at least 5% when the level of inserted twist is changed.
  • the electronically conducting yarn electrode can have an electrochemical capacitance of at least 0.5 Farads per gram of electrochemically-active material.
  • the invention features an electrochemical mechanical energy harvester that includes an electrolyte-containing coiled electronically conducting yarn electrode that is operable to cause reversible changes in electrochemical capacitance when either stretched, twisted, or combinations thereof, thereby enabling the harvesting of either tensile mechanical energy, torsional mechanical energy or a combination of tensile and torsional mechanical energy, as electrical energy.
  • the electrochemical mechanical energy harvester further includes a counter electrode.
  • the electrochemical mechanical energy harvester further includes an electrolyte that ionically connects said electronically conducting electrode and said counter electrode.
  • Implementations of the invention can include one or more of the following features:
  • the electrochemical mechanical energy harvester can be operable to cause a reversible change in open circuit voltage of at least 20 mV when the level of inserted twist is changed.
  • the electronically conducting yarn electrode can be operable to cause the reversible change in electrochemical capacitance of at least 5% when the level of inserted twist is changed.
  • the electronically conducting yarn electrode can have an electrochemical capacitance of at least 0.5 Farads per gram of electrochemically-active material.
  • the invention features a wearable self-generating and storaging packing.
  • the wearable self-generating and storaging packing includes an electrochemical mechanical energy harvester that is a twistron fiber harvester.
  • the wearable self-generating and storaging packing further includes a stretchable fiber supercapacitor.
  • Implementations of the invention can include one or more of the following features:
  • the twistron fiber harvester can include a first fiber that is stretchable, a homochiral CNT yarn wrapped about the first fiber, a heterochiral CNT yarn wrapped about the first fiber, a first solid electrolyte about the first fiber wrapped with the homochiral CNT yarn and the heterochiral CNT yarn, and a first tube about the first solid electrolyte about the fiber wrapped with the homochiral CNT yarn and the heterochiral CNT yarn.
  • the first tube can be stretchable.
  • the stretchable fiber supercapacitor can include a second fiber that is stretchable, an anode including a first substantially non-twisted CNT yarn wrapped about the second fiber, a cathode including a second substantially non-twisted CNT yarn wrapped about the second fiber, a second solid electrolyte about the second fiber wrapped with the anode and the cathode, and a second tube about the second solid electrolyte about the second fiber wrapped with the anode and the cathode.
  • the second tube can be stretchable.
  • the first fiber, the second fiber, the first tube, and the second tube can each include rubber.
  • the wearable self-generating and storaging packing of Claim 74 can include a plurality of twistron fiber harvesters and a plurality of stretchable fiber supercapacitors (SFSCs).
  • SFSCs stretchable fiber supercapacitors
  • FIGS. 1A-1F show twistron harvester configuration, structure, and performance for tensile energy harvesting in 0.1 M HCl.
  • FIG. 1A shows schematic illustrations of cone, funnel, Fermat, and dual-Archimedean spinning, which are used to make twistron harvesters, and the cross sections of the resulting respective yarns.
  • FIG. 1B shows an illustration of a torsional-tethered coiled harvester electrode and counter and reference electrodes in an electrochemical bath, showing the coiled yarn before and after stretch.
  • FIG. 1C provides graphs that show, respectively, the time dependence of the sinusoidal applied tensile strain and the resulting change in open-circuit voltage (OCV) and short-circuit current (SCC) for a cone-spun coiled harvester that is harvesting tensile mechanical energy in a 0.1 M aqueous HCl electrolyte.
  • OCV open-circuit voltage
  • SCC short-circuit current
  • FIG. 1D is a graph that shows capacitance and OCV versus applied tensile strain for a coiled twistron harvester in 0.1 M HCl electrolyte.
  • the inset 112 provides the cyclic voltammogram (CV) curve for 0% strain and 30% strain.
  • FIG. 1E is a graph that shows the frequency dependence of peak power, peak-to-peak OCV, and electrical energy per cycle for 50% stretch of a 8.5% untwisted coiled harvester in 0.1 M HCl electrolyte.
  • FIG. 1F is a graph that shows generated peak voltage and peak power versus load resistance for a coiled yarn and a partially untwisted coiled yarn when stretched at 1 Hz to the maximum reversible elongation.
  • FIGS. 2A-2D show torsional and tensile performance of twistron harvesters.
  • FIG. 2A is a graph that shows the generated peak power and peak voltage versus load resistance for 1 Hz stretch to 30% strain for the cone spun harvester of FIG. 1A and an otherwise identical dual-Archimedean-spun harvester.
  • FIG. 2B is a graph that shows the negligible effect of 30,000 stretch/release cycles on peak power, average power, and electrical energy per cycle for the above twistron yarn, when cycling at 1 Hz to 30% strain in 0.6 M NaCl at 0° C.
  • the inset of FIG. 28 shows output power versus time during typical cycles.
  • FIG. 2C is a graph that shows the dependence of capacitance and electrode potential on isometric twist and untwist for a non-coiled, 47-mm-long, 360- ⁇ m-diameter, cone-spun yarn in 0.1 M HCl.
  • FIG. 2D are graphs that show OCV versus time during 60% stretch in 0.1 M HCl for homochiral and heterochiral cone-spun yarns produced by mandrel coiling on a stretched rubber core, showing opposite stretch-induced voltage responses for the homochiral and heterochiral yarns.
  • the inset of the graph of FIG. 2D illustrate the opposite changes in yarn twist in response to stretch for homochiral and heterochiral coils.
  • FIGS. 3A-3D show piezoelectrochemical spectroscopy and its application for twistron harvesters.
  • FIG. 3A is a graph that shows the cyclic voltammogram (50 mV/s scan rate) of a coiled twistron electrode in 0.1 M HCl during 5 Hz sinusoidal stretch to 10%.
  • FIG. 3B is a graph that shows the magnitude and phase of current fluctuations relative to the applied mechanical stretch.
  • the potential of both the minimum current amplitude and the 180 degree phase shift correspond to the PZC ( ⁇ 58 mV vs. Ag/AgCl).
  • FIG. 3C is a graph that shows OCV (versus PZC) in different electrolytes for 1 Hz strain, indicating the combined effects of chemically-induced charge injection and stretch-induced capacitance change.
  • FIG. 3D is a graph that shows the negligible dependence of PZC on applied tensile strain for increasing and decreasing strain and temperature. The inset of FIG. 3D shows that the PZC varies little with temperature.
  • FIGS. 4A-4D show alternative harvester geometries.
  • FIG. 4A is a graph that shows the peak power and peak output voltage versus load resistance for 1 Hz, 30% stretch of a two-electrode twistron harvester containing an energy-harvesting, coiled CNT yarn working electrode, which is wrapped with a non-harvesting, non-coiled CNT yarn counter electrode.
  • Polyvinyl alcohol (PVA) containing 0.1 M HCl was used to protect the harvester and electronically insulate opposite electrodes.
  • the inset of FIG. 4A shows that the OCV versus time, before and after PVA coating.
  • FIG. 4B is a graph that shows peak-to-peak OCV and peak SCC at 1 Hz and 50% strain for series and parallel connected two-electrode harvesters made from the homochiral and heterochiral yarns.
  • the yarns were coated with 10 wt % PVA/4.5 M LiCl gel electrolyte after being sewn into a textile.
  • the insets of FIG. 4B show low and high magnification photographs of the textile at 0% and 50% strain (scale bar: 1 cm).
  • FIG. 4C is a graph that shows the peak power, average power, and energy per cycle generated by a coiled twistron harvester when mechanically stretched and twisted by an in-series, coiled, 127- ⁇ m-fiber-diameter nylon artificial muscle (located over the electrolyte bath) that converts thermal energy into mechanical energy.
  • the inset of FIG. 4C shows an illustration of twistron up-twist and stretch during muscle heating, and the reverse processes during muscle cooling.
  • FIG. 4D is a graph that shows the frequency dependence of peak power and energy-per-cycle before and after incorporating a Pt wire current collector into a coiled twistron yarn.
  • the inset of FIG. 4D is an SEM image of this harvester (scale bar: 100 ⁇ m) showing the coiled CNT yarn and Pt wire.
  • FIGS. 5A-5D show structural origin of twistron performance and performance comparisons with previously known material-based harvesters.
  • FIG. 5A is a TEM image showing MWNT collapse to increase inter-nanotube van der Waals energy in a MWNT bundle.
  • FIG. 5B is scanning transmission microscope (STEM) image showing the origin of the high capacitance of MWNT bundles.
  • FIGS. 5C-5D are graphs that show peak power ( FIG. 5C ) and frequency-normalized peak power ( FIG. 5D ), respectively, versus the frequency at which this peak power was obtained for present and prior-art technologies for piezoelectric (PZ), electrostatic (ES), triboelectric (TEG), and dielectric elastomer (DEG) generators.
  • PZ piezoelectric
  • ES electrostatic
  • TEG triboelectric
  • DEG dielectric elastomer
  • FIG. 6 shows the voltage and capacitance of a coiled CNT yarn when stretched to 20% strain, and released to ⁇ 75% strain.
  • FIGS. 7A-7C show the results of piezoelectrochemical spectroscopy on a coiled CNT yarn that was treated by nitrogen plasma.
  • FIG. 7A shows cyclic voltammograms of the yarn during 10% sinusoidal stretch at 5 Hz and with no stretch.
  • FIG. 7B shows the difference between the curves in FIG. 7A , to highlight the AC current caused by stretching.
  • FIG. 7C plots the amplitude of the AC current in FIG. 7B as a function of the applied voltage, and extrapolates this trend to predict that the PZC occurs at ⁇ 950 mV vs. Ag/AgCl.
  • FIG. 8 compares the results of piezoelectrochemical spectroscopy on a pristine coiled CNT yarn and on a coiled CNT yarn that was treated by high temperature annealing under tension in vacuum.
  • the PZC of the pristine yarn around ⁇ 80 mV vs. Ag/AgCl, shifts to around ⁇ 250 mV vs. Ag/AgCl.
  • FIG. 9A-9B illustrate the structure of an elastomeric twistron harvester that combines opposite chirality harvester electrodes and the use of such harvesters in a textile that both harvests mechanical energy as electrical energy and stores this energy in supercapacitor yarns.
  • FIG. 9A illustrates a twistron harvester in which twisted fibers of opposite chiralities are wrapped around a rubber fiber core, and then overcoated with gel electrolyte.
  • FIG. 9B depicts a textile woven from yarns of FIG. 9A and fibers made using non-twisted electrodes, which act as supercapacitor yarns for storing energy. These non-twisted electrodes can be connected in parallel to store more charge, while the twisted harvester electrodes can be connected in series to increase generated voltage. The generated AC voltage from the harvesting yarns can be rectified through a diode bridge for storage in the energy storage yarns.
  • FIGS. 10A-10D illustrate the fabrication of a complete harvester yarn which combines opposite chirality harvester electrodes and gel electrolyte along the length of the yarn.
  • the twisted fiber of FIG. 10A is wrapped around a rubber mandrel in alternating directions to make the structure of FIG. 10B .
  • Cutting at the points designated in FIG. 10C and coating with gel electrolyte, as shown in FIG. 10D yields series-connected harvesters along the length of the yarn.
  • FIGS. 11A-11B are illustrations of a self-generating and storaging package of an embodiment of the present invention.
  • FIG. 1A is a configuration of the self-generating and storaging package, which has an energy harvester and supercapacitor based on carbon nanotube (CNT) yarn twist.
  • Each of the harvester and supercapacitor include two CNT yarns, silicone rubber fiber, and solid electrolyte in silicone rubber tube.
  • the energy harvester shown in FIG. 11A includes a homochiral CNT yarn and heterochiral CNT yarn (similar to as shown in FIG. 9A ). When stretching the harvester, the homochiral CNT yarn is twisted and the heterochiral CNT yarn is untwisted.
  • FIG. 11A is a homochiral CNT yarn and heterochiral CNT yarn.
  • 11B is an illustration of the supercapacitor, which includes two non-twisted CNT yarns for anode and cathode. When stretching the supercapacitor, both non-twisted CNT yarns retain essentially constant capacitance, so no electrical energy is generated.
  • FIGS. 12A-12D show characterization of a twisted CNT yarn and the performance of the CNT yarn as an energy harvester.
  • FIG. 12A shows capacitance change and open circuit voltage of a CNT yarn that enwrapping rubber fiber clockwise direction when stretched to 80% strain. Twist insertion of CNT yarn was controlled from ⁇ 2000 (counter clockwise direction) to 2000 (clockwise direction) turns/m. Negative sign of twist insertion represent heterochiral CNT yarn, and positive sign of twist insertion represent homochiral CNT yarn.
  • FIG. 12A shows capacitance change and open circuit voltage of a CNT yarn that enwrapping rubber fiber clockwise direction when stretched to 80% strain. Twist insertion of CNT yarn was controlled from ⁇ 2000 (counter clockwise direction) to 2000 (clockwise direction) turns/m. Negative sign of twist insertion represent heterochiral CNT yarn, and positive sign of twist insertion represent homochiral CNT yarn.
  • FIG. 12A shows capacitance change and open circuit voltage of a CNT
  • FIG. 12B shows capacitance and peak-to-peak open circuit voltage versus strain for the homochiral (squares 1203 and 1205 , respectively) and heterochiral (squares 1204 and 1206 , respectively) CNT yarns enwrapping a rubber fiber.
  • FIG. 12C shows open circuit voltage of one-body energy harvester when stretched using 1 Hz sinusoidal wave to 60% strain.
  • FIG. 12D shows voltage and peak power versus frequency. The inset of FIG. 12D shows voltage and peak power versus load resistance.
  • FIGS. 13A-13F show electrochemical performance of a solid-state MnO 2 /CNT/nylon fiber supercapacitor.
  • FIG. 13A shows cyclic voltammetry curves measured from 100 to 1000 mV/s for a solid-state stretchable fiber supercapacitor (SFSC) coated with solid electrolyte gel (comprising 10 wt % polyvinyl alcohol, PVA, in 0.1 M HCl).
  • FIG. 13B shows galvanostatic charge/discharge curves measured from 1.6 ⁇ A/cm 2 to 16 ⁇ A/cm 2 current densities.
  • FIG. 13A shows cyclic voltammetry curves measured from 100 to 1000 mV/s for a solid-state stretchable fiber supercapacitor (SFSC) coated with solid electrolyte gel (comprising 10 wt % polyvinyl alcohol, PVA, in 0.1 M HCl).
  • FIG. 13B shows galvanostatic charge/discharge
  • FIG. 13C shows calculated linear capacitance (normalized by SFSC length) and areal specific capacitance (normalized by the surface area of SFSC) at scan rate from 100 to 1000 mV/s.
  • FIG. 13D shows static CV curves of a solid-state SFSC for 0 to 60% strains.
  • the insets of FIG. 13D show optical images of the SFSC at 0% and 60% strains.
  • FIGS. 13E-13F show capacitance retention during sinusoidal stretching and 180 degree bending deformation for 1000 cycles. For FIGS. 13E-13F , capacitance was measured after each mechanical deformation cycle.
  • the inset of FIG. 13E shows dynamic CV curves of the solid-state SFSC at 0% strain and 1 Hz stretched to 60% strain.
  • the insets of FIG. 13F shows optical images and CV curve of the solid-state SFSC at 0° and 180° bending state.
  • FIGS. 14A-14C show the performance of a self-generating and storaging package.
  • FIG. 14A shows OC voltage as a function of the number of TFH. Insets of FIG. 14A show optical images of a self-generating and storaging package woven into a glove at 0% and 50% strain.
  • FIG. 14B shows OCV and rectified OCV at 0.75 Hz from a rectification circuit.
  • FIG. 14C shows the time dependence of SFSC voltage when charging three SFSCs connected in parallel.
  • harvesters were produced by spinning sheets of forest-drawn carbon multi-walled nanotubes (MWNT) into high strength yarns (Zhang 2004; Zhang 2005). Due to large MWNT diameters, MWNT bundling, and the absence of pseudo-capacitive redox groups, these yarns have a capacitance of ⁇ 15 F/g (Lepró 2012). By inserting extreme twist into a CNT yarn that supports a weight, coils initiate and propagate, producing a highly elastic, uniformly coiled structure.
  • FIG. 1A illustrates the spinning methods and resulting yarn topologies before the onset of coiling.
  • FIG. 1A illustrates the spinning methods and resulting yarn topologies before the onset of coiling.
  • FIG. 1A are schematic illustrations of cone 101 , funnel 102 , Fermat 103 , and dual-Archimedean 104 spinning, which are used to make twistron harvesters, and the cross sections 105 - 108 of the resulting respective yarns.
  • the harvester yarns had a diameter of 50 to 70 ⁇ m when twisted to just before coiling, and were made by the cone spinning process shown in FIG. 1A .
  • Such harvesters can generally be made from twisted, high-electrochemical-surface-area, conductive yarn, where “high-electrochemical-surface-area” yarns are yarns which are capable of providing at least 0.1 Farads per gram of active material.
  • FIG. 1B illustrates the electrochemical cell used for the initial characterization of harvester yarns, which comprises a coiled MWNT yarn working electrode, a high-surface-area counter electrode, and a reference electrode that are immersed in aqueous electrolyte.
  • FIG. 1B shows an illustration of a torsional-tethered coiled harvester electrode and counter and reference electrodes in an electrochemical bath 105 a , showing the coiled yarn before and after stretch (yarn 106 a and yarns 106 b , respectively).
  • FIG. 1C provides graphs 107 - 109 that show, respectively, the time dependence of the sinusoidal applied tensile strain and the resulting change in open-circuit voltage (OCV) and short-circuit current (SCC) for a cone-spun coiled harvester that is harvesting tensile mechanical energy in a 0.1 M aqueous HCl electrolyte.
  • FIG. 1C shows the time dependence of open-circuit voltage (OCV) and short circuit current (SCC) generated by a coiled cone-spun harvester during 1 Hz sinusoidal stretch to 30% strain in 0.1 M HCl electrolyte. This sinusoidal stretch does not generally produce sinusoidal variation in OCV or SCC.
  • 1D which is a graph that shows capacitance and OCV versus applied tensile strain for a coiled twistron harvester in 0.1 M HCl electrolyte (plots 110 - 111 , respectively, with the inset 112 providing the cyclic voltammogram (CV) curve for 0% strain and 30% strain (plots 113 - 114 , respectively)).
  • the electrolyte was 0.1 M HCl
  • the reference electrode was Ag/AgCl
  • the applied strain was sinusoidal. Applied tensile stresses were normalized to the cross-sectional area of the twisted, non-coiled yarn.
  • FIG. 6 shows the capacitance and voltage change (plots 601 - 602 , respectfully) resulting from stretching a coiled CNT yarn from 20% to ⁇ 75% strain, wherein 0% strain is defined as the minimum strain at which the coiled yarn is straight and a negative strain corresponds to an additional contraction below this point which can result in the coiled yarn undergoing snarling
  • FIG. 1E shows the frequency dependence of peak power (plot 115 ), peak-to-peak OCV (plot 116 ), and electrical energy per cycle (plot 117 ) for 50% stretch of an 8.5% untwisted coiled harvester in 0.1 M HCl electrolyte.
  • FIG. 1F shows the generated peak voltage versus load resistance for the coiled yarn (plot 118 ) and the partially untwisted coiled yarn (plot 119 ) when stretched at 1 Hz to the maximum reversible elongation.
  • FIG. 1F further shows peak power versus load resistance for the coiled yarn (plot 120 ) and the partially untwisted coiled yarn (plot 121 ) again when stretched at 1 Hz to the maximum reversible elongation.
  • the non-strained capacitance increased from 3.97 to 6.50 F/g, indicating a 64% increase in electrochemically accessible surface area.
  • this twist removal increased peak power by a factor of 1.4 (to 179 W/kg at 12 Hz, FIG. 1E ) and increased maximum output energy per cycle by a factor of 2.9 (to 41.2 J/kg at 0.25 Hz).
  • the existence of a long plateau in frequencies that maximize power (from 12 Hz to above 25 Hz in FIG. 1E ) provides a major advantage compared to resonant harvesters, whose power output rapidly degrade as mechanical deformation frequencies deviate from resonance (Jaffe 1971).
  • FIG. 2A show, respectively, the generated peak power and peak voltage versus load resistance for 1 Hz stretch to 30% strain for the cone spun harvester of FIG. 1A .
  • Plots 203 - 204 in FIG. 2A show, respectively, the generated peak power and peak voltage versus load resistance for 1 Hz stretch to 30% strain for an otherwise identical dual-Archimedean-spun harvester.
  • This stress non-uniformity was avoided by cone spinning ( FIG. 1A ), which involves rolling a CNT sheet stack about the CNT alignment direction to make a cylinder. By twisting this cylinder around its central axis to produce two cones, which densify to a yarn, stress is evenly distributed during spinning.
  • this cone spinning process was used to make coiled twistron harvesters. Similar performance was obtained by spinning methods that maintain quasi-uniform tension across the CNT array (TABLE 1), such as by (1) tow spinning by inserting twist into an oriented yarn obtained by collapsing a sheet using lateral pressure (or liquid-based densification) or (2) ‘funnel spinning’, wherein yarn is spun by drawing and twisting along the axis of a cylindrical CNT forest (or a cylindrically positioned array of CNT forests). Direct spinning from a CNT forest to produce a ‘Fermat’ yarn structure (Lima 2011) provided yarns with similarly high energy harvesting performance.
  • the mechanical load applied during twisting determines the coil spring index, which affects harvester performance.
  • the peak power and change in capacitance for a given percent strain were found to depend on the spring index (measured after coiling, with the coiling load still applied), with a spring index of ⁇ 0.43 yielding the highest peak power (41.3 W/kg for 30% strain at 1 Hz).
  • the spring index increases, the maximum reversible coil deformation increases (and the coil stiffness decreases), which enables energy harvesting over a larger strain range. This tunability allows the twistron harvester to be customized for the stroke range needed for a particular application. Unless otherwise indicated a spring index of ⁇ 0.43 was used for all experiments.
  • FIG. 2B is a graph that shows in plots 205 - 206 , respectively, the negligible effect of 30,000 stretch/release cycles on peak power, average power, and electrical energy per cycle for the above twistron yarn, when cycling at 1 Hz to 30% strain in 0.6 M NaCl at 0° C.
  • Inset 208 of FIG. 2B shows output power versus time during typical cycles.
  • FIG. 2B shows that the peak power and average power at 0° C. (46.3 and 15.3 W/kg) were maintained for over 30,000 cycles at 1 Hz to 30% strain in 0.6 M NaCl.
  • gravimetric energy output per cycle is scale invariant.
  • the amount of inserted twist (T, in turns per meter) was scaled inversely with yarn diameter D to keep TD constant. This structural scaling automatically occurred, since yarns were twisted under the same stress until fully coiled, and 77) was scale invariant for this degree of inserted twist.
  • the obtained spring index (presently 0.43) was scale invariant.
  • the per-cycle gravimetric energy, peak-to-peak OCV, and the frequency dependence of gravimetric peak power were found to be constant for yarn diameters between 40 and 110 ⁇ m. Also, a similar peak power density was obtained at 1 Hz for a coiled yarn and a four-ply yarn made from this coiled yarn.
  • twist changes induce the capacitance changes that enable mechanical energy harvesting.
  • these devices are referred to as “twistron” harvesters, using “twist” to denote the harvester mechanism and “tron,” which is the Greek suffix for device.
  • the twist mechanism for energy harvesting by stretching a coiled yarn was first suggested by the observation that twisting a non-coiled yarn generated electrical energy. It has been found that for isometric (constant length) and isobaric (constant force) twist insertion, twist insertion reversibly decreases the electrochemical capacitance and increases the OCV (the results for isometric twist insertion are shown respectively in plots 209 - 210 in FIG. 2C ). The change in OCV is larger (86.8 mV) for isometric twist insertion than for isobaric twist insertion (43.6 mV), likely reflecting yarn densification and associated capacitance decrease during isobaric loading.
  • FIG. 2D show OCV versus time during 60% stretch in 0.1 M HCl for homochiral and heterochiral cone-spun yarns produced by mandrel coiling on a stretched rubber core, showing opposite stretch-induced voltage responses for the homochiral and heterochiral yarns (in, respectively graphs 211 - 212 ).
  • the respective insets 213 - 214 in the graphs 211 - 212 of FIG. 2D illustrate the opposite changes in yarn twist in response to stretch for homochiral and heterochiral coils.
  • Power output can be increased by simultaneously using working and counter electrodes as energy harvesters. For instance, simple mechanical jigs can convert motion into an out-of-phase tensile deformation of two otherwise identical yarn electrodes, thereby doubling harvester voltage. This need to convert mechanical stretch to elongation of one electrode and release of stretch on the opposite electrode can be avoided by simultaneously stretching a homochiral yarn electrode and a heterochiral yarn counter electrode ( FIG. 2D ). Since yarn coiling and twist can irreversibly cancel when stretching an unsupported heterochiral yarn, these experiments utilized harvester yarns that are wrapped around a rubber fiber core, which acts as a return spring to prevent this irreversibility.
  • piezoelectrochemical spectroscopy involves characterizing an electrode by cyclic voltammetry (CV) while simultaneously stretching the electrode sinusoidally. By comparing this CV to a baseline scan without deformation, the AC current generated by the electrode can be determined as a function of applied voltage. This is shown in FIG. 3A , where CV scans for 0% strain and 5 Hz (plots 301 - 302 , respectively) stretch to 10% strain are overlaid. Using a lock-in method, the magnitude and phase of the AC current with respect to the mechanical excitation are obtained as a function of voltage (plots 303 - 304 of FIG. 3B , respectively).
  • the PZC corresponds to the potential of minimum AC current. Furthermore, as shown in plot 304 , the phase of the AC current with respect to the mechanical excitation inverts by 180° at the PZC, which is consistent with the yarn having positive net charge at potentials above the PZC and negative charge below the PZC.
  • PECS shows that the PZC changes by less than ⁇ 5 mV when a coiled twistron harvester is stretched by 20%. This result is very important, since it indicates that the charge injected by the electrolyte is largely strain independent ( FIG. 3D ).
  • FIG. 3D shows the negligible dependence of PZC on applied tensile strain for increasing and decreasing strain (plots 310 - 311 , respectively) and temperature (plot 313 in inset 312 ).
  • the twistron harvesters can be used as self-powered strain sensors.
  • the open-circuit potential for a give deformation depends on strain frequency/rate, which can be compensated for to provide the most accurate measurements of strain when the deformation rate is high.
  • the intrinsic bias voltage of the CNT yarn is calculated by subtracting the PZC from the OCV of the non-strained yarn.
  • FIG. 3C show that the bias voltage for coiled yarn decreases with increasing pH, from 0.4 V for 0.1 M HCl (plot 306 ) and 0.28 V for 0.1 M HBr (plot 307 ) (both with pH 1) to 0.1 V for 0.6 M NaCl (pH 7) (plot 308 ), and to ⁇ 0.25 V for 0.1 M KOH (pH 13) (plot 309 ).
  • a low pH electrolyte is hole injecting and a high pH electrolyte is electron injecting.
  • bias voltage depends upon the specific electrolyte, even at the same pH, a linear dependence of bias voltage on pH was obtained ( ⁇ 47 mV per pH unit for aqueous HCl), which is consistent with the ⁇ 59 mV per pH unit theoretically predicted by the Nernst equation (Tanaka 2009).
  • the direction of OCV change with applied tensile strain depends upon whether the electrolyte provides a positive or negative bias potential ( FIG. 3C ).
  • the OCV and peak power were maximized for 0.1 M HCl concentration and for 0.6 M NaCl concentration.
  • the PZC of coiled CNT yarn harvesters can also be modified by chemical of physical processing. For instance, by treating CNT sheet stacks in nitrogen plasma prior to twisting and coiling, the effective PZC was found to shift from the usual ⁇ 50 mV to ⁇ 150 mV vs. Ag/AgCl of pristine yarns to ⁇ 950 mV vs. Ag/AgCl, as seen in FIG. 7A-7C .
  • FIG. 7A shows cyclic voltammograms of the yarn during 10% sinusoidal stretch at 5 Hz and with no stretch (plots 701 - 702 , respectively).
  • FIG. 7B shows in plot 703 the difference between the curves in FIG. 7A , to highlight the AC current caused by stretching.
  • FIG. 7A shows cyclic voltammograms of the yarn during 10% sinusoidal stretch at 5 Hz and with no stretch (plots 701 - 702 , respectively).
  • FIG. 7B shows in plot 703 the difference between the curve
  • annealing the yarn under tension at high temperature via a process referred to as the incandescent tension anneal process (ITAP) was shown to lower the PZC of a coiled CNT yarn electrode to around ⁇ 250 mV vs. Ag/AgCl, as shown in FIG. 8 (with plots 801 - 802 for the pristine yarn and the ITAP yarn, respectively).
  • ITAP incandescent tension anneal process
  • TEM images of individual MWNTs in twistron yarn provide a gravimetric surface area of 242 m 2 /g and a calculated capacitance of 9.7 F/g for the hypothetical case where none of the MWNTs in the yarn are in bundles.
  • This calculated capacitance for non-bundled MWNTs is surprisingly close to that measured for the twistron harvester in FIG. 2C and for a similar non-twisted yarn (5.8 F/g for the partially twisted and 8.3 F/g for the non-twisted torsional harvester, respectively).
  • FIG. 5C-5D show peak power ( FIG. 5C ) and frequency-normalized peak power ( FIG. 5D ), respectively, versus the frequency at which this peak power was obtained for present technologies 506 and prior-art technologies for piezoelectric (PZ) 501 , electrostatic (ES) 502 , triboelectric (TEG) 503 , and dielectric elastomer (DEG) 505 generators.
  • PZ piezoelectric
  • ES electrostatic
  • TEG triboelectric
  • DEG dielectric elastomer
  • the MWNTs in large bundles are so irregularly packed that an individual MWNT likely meanders from side-to-side in a bundle. Twist-induced tension in a bundle might increase the packing density by decreasing this meandering, thereby decreasing the accessible intra-bundle capacitance.
  • the measured rate dependence of capacitance over six orders of magnitude in potential scan rate suggests the possibility that both bundle surface and intra-bundle capacitances contribute at slow scan rates.
  • FIGS. 1C-1D and other experimental results show that only a fraction of the mechanically-induced capacitance change is used for harvesting electrical energy in some yarn samples.
  • this fraction is the ratio of the product of OCV and the capacitance after twistron deformation to this product before deformation.
  • the fraction of capacitance change that is useful for energy harvesting varies from 79.0% to 99.5% for torsional and tensile energy harvesters. This up to 21.0% of non-productive capacitance change is likely due to counter ions being trapped in void spaces that lose contact with the bulk electrolyte during twist, which prevents their associated charge from redistributing onto electrochemically-accessible surfaces to increase electrode voltage.
  • Twistron harvesters having harvesting electrode diameters between 10 ⁇ m and 500 ⁇ m are especially useful for most applications, because very large diameter harvesting electrode diameters severely limit their ability to harvest energy from rapid changes in harvester length or the amount of yarn twist (due to the need for ion diffusion over large distances in the yarn diameter).
  • Unlimited numbers of twistrons, comprising small diameter electrodes can be operated in parallel to generate giant amounts of power. While smaller yarn diameters can provide useful responses, the cost of twist insertion to provide useful performance increases with decreasing yarn diameter.
  • 150-nm-dimeter twisted carbon nanotubes can be spun as twistron harvesters that are deployable for energy harvesting and sensing on the nanoscale. A method for fabricating twisted 150 nm diameter carbon nanotube yarns has been previously described (Li 2011).
  • FIG. 4A shows in plots 401 - 402 , respectively, the peak power and peak output voltage versus load resistance for 1 Hz, 30% stretch of a two-electrode twistron harvester containing an energy-harvesting, coiled CNT yarn working electrode, which is wrapped with a non-harvesting, non-coiled CNT yarn counter electrode.
  • Polyvinyl alcohol (PVA) containing 0.1 M HCl was used to protect the harvester and electronically insulate opposite electrodes.
  • Inset 403 of FIG. 4A shows that the OCV versus time, before and after PVA coating (plots 404 - 405 , respectively).
  • harvesters comprising electrodes that undergo opposite voltage changes when stretched were produced.
  • two CNT sheet stacks were cone-spun in opposite twist directions until just before the onset of coiling. Both electrodes were then coiled in identical directions around 300%-elongated, 0.5-mm-diameter rubber mandrels, so that one electrode increases density and the second decreases density when stretched.
  • These homochiral and heterochiral electrodes were then separately overcoated with PVA/HCl electrolyte, placed parallel (separated by ⁇ 1.5 mm), and finally jointly overcoated with additional PVA/HCl electrolyte.
  • FIG. 4B shows peak-to-peak OCV and peak SCC at 1 Hz and 50% strain for series (plot 406 ) and parallel (plot 407 ) connected two-electrode harvesters made from the homochiral and heterochiral yarns.
  • the yarns were coated with 10 wt % PVA/4.5 M LiCl gel electrolyte after being sewn into a textile.
  • Insets 408 - 409 of FIG. 4B show low magnification photographs of the textile at 0% and 50% strain (scale bar: 1 cm), respectively.
  • Insets 410 - 411 are the corresponding high magnification photographs.
  • FIG. 9A shows the use of two oppositely-twisted CNT yarns (homochiral CNT yarn 902 and heterochiral CNT yarn 903 ), wrapped around a rubber fiber 901 in the same direction, to provide a single stretchable composite fiber 900 that incorporates both homochiral and heterochiral yarn electrodes.
  • a layer of gel electrolyte is added to coat the two yarns. When stretched, the voltage of the homochiral yarn increases, while the voltage of the heterochiral yarn decreases, generating an increased voltage difference between the two yarns.
  • FIG. 9B shows a schematic of an exemplary textile that is woven with energy harvesting yarns 905 (such as yarns 900 shown in FIG. 9A ) in one direction and energy storing yarns 906 in the other direction. These yarns can be connected in series ( 907 ) or parallel ( 908 ) to optimize the voltage and current characteristics of the harvester and storage yarns, and a diode bridge 909 could be used to convert AC harvester voltage directly into DC voltage for storing in the capacitor yarns.
  • FIG. 10A-10D show another example architecture for producing a single rubber fiber harvester that incorporates both homochiral and heterochiral electrodes, and allows for easy serial connection to increase output voltage.
  • a spool of twisted CNT yarn 1002 is prepared for wrapping around a rubber mandrel 1001 . Wrapping the CNT yarn around mandrel into the pattern shown in FIG. 10B creates alternating bands of homochiral and heterochiral harvesters. Cutting the connecting yarn at cutting points 1003 , such as shown in FIG. 10C , separates these homochiral and heterochiral segments so they can act as separate electrodes that increase voltage and decrease voltage, respectively, during stretch.
  • Bridging the separate homochiral and heterochiral regions with a gel electrolyte 1004 creates multiple individual harvester cells along the length of the yarn.
  • the built-in series connection of these yarns provides the ability to scale output voltage by increasing the length of the yarn.
  • the output voltages from these harvesters can be combined in-series or in-parallel for application as self-powered strain sensors or mechanical energy harvesters.
  • the application of the twistron harvester of FIG. 2D and FIG. 4B as a self-powered solid-state strain sensor that is sewn into a shirt and used for monitoring breathing was demonstrated. When strained by ⁇ 10% during breathing, this 3-cm-long twistron sensor generated ⁇ 16 mV.
  • FIG. 4C shows the peak power (plot 412 ), average power (plot 413 ), and energy per cycle (plot 414 ) generated by a coiled twistron harvester when mechanically stretched and twisted by an in-series, coiled, 127- ⁇ m-fiber-diameter nylon artificial muscle (located over the electrolyte bath) that converts thermal energy into mechanical energy.
  • Inset 415 of FIG. 4C shows twistron up-twist and stretch 416 during muscle heating, and the reverse processes 417 during muscle cooling.
  • this corresponds to a harvested peak power and average power during heating of 1.41 W/kg and 0.86 W/kg, respectively, and a full-cycle average electrical power of 0.29 W/kg, compared to 0.015 W/kg for a polymer muscle connected to an electromagnetic generator (Kim 2015).
  • Small fluctuations in ambient temperature can be harvested by increasing the length of the polymer muscle, such as by using pulleys to minimize total package size, or by using large spring index polymer muscle coils to maximize stroke (Haines 2014).
  • a coiled twistron harvester was used to harvest the energy of near-shore ocean waves. Both the energy harvesting twistron yarn and the Pt mesh/CNT counter electrode were directly immersed in Gyeonpo Sea of Korea, where the ocean temperature was 13° C., the wave frequency during the study ranged from 0.9 to 1.2 Hz, and the NaCl content in the sea water was 0.31 M. The top of the twistron yarn was attached to a balloon and the bottom was rested on the seabed by attaching to a sinker.
  • our harvester yarns can provide these voltages if multiple harvesters are combined in series to increase their voltage, as in FIG. 4B , or by using commercially-available circuits to transform the voltage of individual harvesters.
  • a voltage step-up converter Linear Technologies LTC3108 was used to convert the voltage of a single coiled harvester electrode (weighing 19.2 mg) from ⁇ 80 mV up to 2.8 V to charge a 5 ⁇ F capacitor. This harvester/converter was used to power a green LED, which lights up to indicate every time the harvester yarn is stretched.
  • FIG. 4D shows the peak power for 50% stretch at 12 Hz from 170 W/kg ( FIG. 1E ) to 250 W/kg ( FIG. 4D ) by coiling a 23- ⁇ m-diameter Pt wire within the coiled twistron yarn.
  • FIG. 4D shows the frequency dependence of peak power before and after incorporating the Pt wire current collector into the coiled twistron yarn (plots 418 - 419 , respectively).
  • FIG. 4D further shows the corresponding energy-per-cycle before and after incorporating the Pt wire current collector into the coiled twistron yarn (plots 420 - 421 , respectively).
  • Inset 422 of FIG. 41 ) is an SEM image of this harvester (scale bar: 100 ⁇ m) showing the coiled CNT yarn 423 and Pt wire 424 .
  • non-twisted yarns can be used for harvesting torsional mechanical energy, since the energy harvesting process provides twist insertion and twist removal.
  • Coiled yarns are most useful for harvesting tensile mechanical energy, since non-twisted or twisted, non-coiled yarns harvest relatively negligible tensile mechanical energy as electrical energy. Since these yarns typically have high conductivity of 300 S/cm or above, the energy harvesters and supercapacitors are not required to have separate current collectors, making it possible to decrease device weight and volume and simplify device construction, unlike the case for other harvesters and supercapacitors.
  • the results of FIG. 4D show that twistron performance can be enhanced by using an incorporated metal wire to decrease the resistance of the twistron harvester.
  • the twistron harvester of the present invention can be utilized for wearable device using diameter, length, and series/parallel connection.
  • the configuration can include working and counter electrodes in a one-body fiber.
  • Embodiments of the present invention include configurations of stretchable and flexible one-body twistron fiber harvester (TFH). Advances resulted from adding and second type of chirality to CNT yarns that are highly twisted before coiling. Furthermore, since CNT are known as supercapacitor materials, flexible, stretchable fiber supercapacitor (SFSC) can be utilized in self-powered packages composed of TFH and SFSC as shown in FIG. 11A .
  • FIG. 11A flexible, stretchable fiber supercapacitor
  • FIG. 11A shows a self-generating and storaging package 1101 that includes twistron fiber harvesters (TFH) 1102 and stretchable fiber supercapacitors (SFSCs) 1103 .
  • the TFH 1102 includes a fiber 1108 (such as a silicone rubber fiber) that has a homochiral CNT yarn 1107 and a heterochiral CNT yarn wrapped about it by coiling, similar to as described above for the stretchable composite fiber 900 shown above in FIG. 9A .
  • the TFH 1102 further has a solid electrolyte 1105 and a silicone rubber tube 1104 .
  • the SFSC 1103 also includes a fiber 1108 (such as a silicone rubber fiber) that has an anode 1110 and cathode 1109 , which are both non-twisted CNT yarns. Like the TFH 1102 , the SFSC 1103 further has a solid electrolyte 1105 , such as the PVA-based gel electrolytes described earlier, and a silicone rubber tube 1104 .
  • a fiber 1108 such as a silicone rubber fiber
  • anode 1110 and cathode 1109 which are both non-twisted CNT yarns.
  • the SFSC 1103 further has a solid electrolyte 1105 , such as the PVA-based gel electrolytes described earlier, and a silicone rubber tube 1104 .
  • Solid state electrolytes are especially important for twistrons and supercapacitors used in textiles, and are also important for many of the other applications described.
  • Examples of solid state electrolytes that are especially useful for invention embodiments are gels comprising a hydrophilic polymer that contains an aqueous solution of an acid, a base, a salt, a mixture of an acid and a salt, or a mixture of a base and a salt.
  • Examples are a gel comprising 10 weight % (wt %) polyvinyl alcohol (PVA) in 0.1M HCl, which was used for a twistron harvester whose performance is presented in FIG. 4A , for the twistron harvesters that were sewn into the textile of FIG.
  • a solid state gel electrolyte that comprises a salt dissolved in water
  • a 10 wt % PVA/4.5 M LiCl gel electrolyte was used as a coating for the twistron harvesters of FIG. 4B , after the harvester electrodes were sewn into a textile.
  • the ionic conductivity of this gel enabled ion flow between adjacent twistron harvester electrodes.
  • a polyurethane-coated, non-coiled, twisted MWNT yarn was wrapped around a self-coiled MWNT yarn, which does the energy harvesting.
  • the deployed polyurethane (PU) (Hydromed D4, from AdvanSource Biomaterials), which was used to prevent inter-electrode shorting in the solid-state twistron, is hydrophilic. Though this PU is not ionically conducting in the dry state, it expands when exposed to 0.1 M HCl as it absorbs up to 50 wt % water, allowing the free flow of ions.
  • CNT yarn electrodes When CNT yarn electrodes are coiled on an elastomeric mandrel fiber for use as supercapacitors for storing harvested energy, these yarns can usefully comprise non-twisted CNT yarns or CNT yarns having low degrees of twist, since elongation of the mandrel fiber will produce little change in capacitance.
  • elastic-mandrel-coiled tensile energy harvesters can be usefully made from CNT yarns that are highly twisted under tension to just below the twist needed to cause coiling.
  • a twistron fiber harvester was fabricated from highly twisted yarns by helically wrapping the yarn on a silicone rubber fiber.
  • S yarn CNT yarn twisted in a clockwise direction when viewed from above
  • Z yarn CNT yarn twisted in a counter-clockwise direction when viewed from above
  • both S yarn and Z yarn were wound in the same clockwise direction around a 250 ⁇ m diameter rubber mandrel, which was stretched by 300%, similar to that shown in FIG. 9A .
  • Coiling a S yarn by wrapping a rubber fiber in a clockwise direction produces a homochiral yarn (in which yarn twist and yarn winding around the rubber fiber have the same chirality) and coiling a Z yarn by wrapping a rubber fiber in a clockwise direction produces a heterochiral yarn (in which yarn twist and yarn wrapping around the rubber fiber have opposite chirality). Since homochiral yarns and heterochiral yarns undergo opposite voltage changes when stretched, both yarns contribute to harvesting when they are stretched on the same elastically deformed mandrel.
  • SFSCs Flexible, stretchable fiber supercapacitors
  • the supercapacitors used for energy storage can either be non-stretchable or stretchable, and can even be a second array of twistron harvesters that serve as supercapacitors.
  • twistron harvesters can be used as harvesters when they are stretched in an application mode and as supercapacitors when they are not stretched in this application mode.
  • stretchable or non-stretchable fibers that serve as batteries can be used to store the energy generated by the twistron harvesters, depending upon whether or not these fiber batteries are stretched during the application.
  • FIG. 12A shows the twist dependence of percent capacitance change (plot 1201 ) and peak-to-peak open circuit voltage (plot 1202 ) of the homochiral and heterochiral CNT yarns that is measured for 80% strain change.
  • a negative twist insertion and a positive twist insertion in these plots corresponds to Z and S directions of twist.
  • a negative sign of twist insertion (region 1214 ) is for a heterochiral CNT yarn and positive sign of twist insertion (region 1215 ) is for a homochiral CNT yarn.
  • the homochiral yarn has ⁇ 36.4% change of capacitance and a 25.9 mV peak-to-peak open circuit voltage (OCV), and the heterochiral yarn has an 18.2% capacitance change and a ⁇ 14.3 mV peak-to-peak OCV.
  • Plots 1203 - 1204 of FIG. 12B show capacitance versus strain of, respectively, the homochiral and heterochiral CNT yarn enwrapping rubber.
  • Plots 1205 - 1206 of FIG. 12B show peak-to-peak open circuit voltage versus strain of, respectively, the homochiral and heterochiral CNT yarn enwrapping rubber.
  • stretch-induced OCV change of the homochiral yarn is larger than for the heterochiral yarn, as shown in FIG. 12B .
  • the reason is that stretch-induced density changes of homochiral and heterochiral yarns were different.
  • the density of homochiral yarn increased by 16.1% (during up-twist), while the density of the heterochiral yarn decreased by 7.4% from 1.21 g/cm 3 to 1.12 g/cm 3 (untwist).
  • FIG. 12C shows the open circuit voltage of a one-body energy harvester with sinusoidal 60% strain at 1 Hz frequency (graphs 1207 - 1208 , respectively).
  • Plots 1209 - 1210 in FIG. 12D show, respectively, voltage and peak power versus frequency for the load resistance that maximizes power output.
  • Plots 1212 - 1213 of inset 1211 of FIG. 12D show, respectively, voltage and peak power versus load resistance.
  • FIGS. 12A-12B were measured for a three-electrode electrochemical cell in 0.1 M HCl electrolyte (working electrode: CNT yarn; counter electrode: Pt/CNT buckypaper, reference electrode: Ag/AgCl).
  • Capacitance was measured from 0.3 to 0.6 V (Ag/AgCl) for a scan rate of 50 mV/s.
  • FIGS. 12C-12D were measured for a two-stretched-electrode electrochemical cell in 0.1 M HCl/PVA 10 wt % solid electrolyte (working electrode: homochiral CNT yarn; counter electrode: heterochiral CNT yarn).
  • a modified one-body TFH was fabricated, comprising solid electrolyte gel in the yarn interiors (10 wt % polyvinyl alcohol, PVA, in 0.1 M HCl), S and Z yarns ( 1106 and 1107 ) that are coated with an ionically conducting polyurethane gel ( 1105 ), an inner silicone rubber fiber ( 1108 ), and a protective outer silicone rubber tube ( 1104 ), as shown in FIG. 11A .
  • the polyurethane was used to prevent shorting between S and Z yarns, and allows ions to penetrate into the CNT yarn by absorbing solid electrolyte.
  • S yarn and Z yarns enwrap rubber fibers in the same direction, which serve as working and counter electrodes, respectively.
  • the modified one-body TFH can generate similar voltage and power compared with above reported twistron harvesters comprising laterally separated homochiral and heterochiral yarns ( FIG. 4B ).
  • FIG. 11A shows a SFSC containing solid electrolyte gel (10 wt % polyvinyl alcohol, PVA, in 0.1 M HCl) within slightly twisted anode and cathode CNT yarns, which are separately coated with polyurethane electrolyte. Both yarns are wrapped on the same silicone rubber fiber, and the total yarn assembly is within a silicone tube.
  • the SFSC can store electrical energy during mechanical deformation for wearable applications without providing a potential change during stretch.
  • FIGS. 13A-13F show the electrochemical energy storage performance of a SFSC in solid electrolyte gel (10 wt % PVA/HCl).
  • the cyclic voltammetry curves measured by various scan rates from 100 to 1000 mV/s, and galvanostatic charge-discharge curves for various current densities from 1.6 to 16 ⁇ A/cm 2 are shown in FIGS. 13A and 13B , respectively.
  • FIG. 13A shows CV curves measured from 100 to 1000 mV/s for a solid-state stretchable fiber supercapacitor (SFSC) coated with solid electrolyte gel (comprising 10 wt % polyvinyl alcohol, PVA, in 0.1 M HCl).
  • SFSC solid-state stretchable fiber supercapacitor
  • Plots 1301 - 1305 correspond to, respectively, 100, 300, 500, 700, and 1000 mV/s.
  • FIG. 13B shows galvanostatic charge/discharge curves measured for current densities from 1.6 ⁇ A/cm 2 to 16 MA/cm 2 .
  • Plots 1306 - 1308 correspond to current densities of 1.6, 4.8, and 16 ⁇ A/cm 2 , respectively.
  • the SFSC had area-normalized and length-normalized capacitances of 73.8 ⁇ F/cm 2 and 1.8 ⁇ F/cm, respectively, at a potential scan rate of 100 mV/s, and had 70.6% capacitance retention in going from a scan rate of 100 mV/s to 1000 mV/s ( FIG. 13C ).
  • FIG. 13C shows the calculated linear capacitance (plot 1309 , normalized by SFSC length) and areal specific capacitance (plot 1310 , normalized by the surface area of the SFSC) at scan rates from 100 to 1000 mV/s.
  • the SFSC shows less than 10% capacitance change (from 1.04 to 0.94 F/g) for a strain range from 0 to 60% ( FIG. 13D ), and excellent capacitance retention during this 60% strain dynamic sinusoidal stretching and during 180 degree bending deformation for 1000 cycles, as shown in FIGS. 13E-13F , respectively.
  • FIG. 13D shows static CV curves for a solid-state SFSC at different strains (0 to 60%).
  • Plots 1312 - 1317 correspond to 0%, 10%, 20%, 30%, 40%, 50%, and 60% strain, respectively.
  • Insets 1318 - 1319 of FIG. 13D show optical images of SFSC at 0% and 60% strains, respectively.
  • FIGS. 13E-13F the plots 1320 and 1324 show capacitance retention during sinusoidal stretching and 180 degree bending mechanical deformation for 1000 cycles, respectively.
  • capacitance was measured after mechanical deformation.
  • Inset 1321 of FIG. 13E shows CV curves for the solid-state SFSC at 10% strain (Plot 1322 ) and during 1 Hz stretching to 60% strain (plot 1323 ).
  • Insets 1328 - 1329 of FIG. 13F show optical images of SFSC before and after 180° of bending, respectively.
  • Plots 1326 - 1327 of inset 1325 show CV curves of the solid-state SFSC before and after 180 degree bending.
  • the CV curves of FIGS. 13D-13F were measured using a potential scan rate of 50 mV/s.
  • SFSC has smaller capacitance than other stretchable supercapacitors, it provides CV curves that are little effected by periodic stretch between 0% and 60% strain at 1 Hz (Insert 1321 of FIG. 13E ). Also, it is generally important to configure the anode and cathode of supercapacitor to prevent electrical shorting.
  • Several supercapacitor fibers, made using two-ply or parallel anode and cathode configurations, have shorting problems during mechanical deformation. In these regards, the present configuration of SFSC has the advantage of preventing shorting between anode and cathode during mechanical deformation, since both yarn electrodes are helically wound in parallel on the same rubber fiber core.
  • THF and SFSC are woven into a textile with energy harvesting yarns 905 (such as yarns 900 shown in FIG. 9A ) in one direction and energy storing yarns 906 in the other direction, as shown in FIG. 9B .
  • energy harvesting yarns 905 such as yarns 900 shown in FIG. 9A
  • energy storing yarns 906 in the other direction, as shown in FIG. 9B .
  • the THFs are connected in series, while the SFSCs are connected in parallel to increase the amount of stored electrical charge ( FIG. 14A ).
  • FIG. 14A shows a picture of an electricity generating and storing package 1403 (size: width: 5 cm; height: 2 cm), which was woven into a commercial glove 1402 .
  • This package comprised 21 THFs in the longitudinal direction and 3-SFSCss in the transverse direction. When THFs were connected in series (up to 21), the output voltage increased in proportion to the number of TFHs up to 600 mV when stretched to 50% strain (plot 1401 ).
  • Insets 1404 a - 1404 b of FIG. 14A (which are magnified images of box 1404 of package 1403 ) show optical images of an electricity generating and storing package at 0% and 50% strains.
  • FIG. 14B shows, respectively, the OCV and the rectified voltage from 21 THFs connected in series. Since the series voltage of this initial demonstration was only 600 mV, the combined voltage drop across two IN5817 diodes used in the bridge rectifier decreased the output to just 30 mV.
  • FIG. 14C shows that SFSCs were charged by the rectified electrical voltage. As shown in plot 1407 , the voltage across the SFSCs (45 ⁇ F) reached 18.8 mV within 18.3 seconds when the THF were sinusoidally stretched at 2-3 Hz to 50% strain. Adding additional harvesters in series or using diodes with a lower voltage drop would allow a greater voltage to charge the SFSCs.
  • the present combined energy harvesting and storing package based on CNT yarns is attractive compared with individual electrolyte-bath-immersed energy harvesting yarns, the realized output electrical energy and stored electrical energy is relatively small.
  • the electrical voltage output can be increased by increasing the number of THFs that are connected in series. Connecting 40 THFs in series can produce a rectified voltage of IV.
  • the energy storage capability of SFSCs can be improved by various methods, such as serial connection, parallel connection, biscrolling with pseudocapacitor materials, or coated with pseudocapacitor materials.
  • invention embodiments are applicable to twisted or coiled twistron harvesters for which the harvesting electrode or electrodes comprise conducting components in addition to, or instead of, carbon nanotubes.
  • graphene can be incorporated within a twisted or coiled CNT yarn by using a process called “biscrolling” (Lima 2011).
  • biscrolling a guest material is deposited onto a sheet of nanofibers or microfibers, and thereafter the sheet is twisted to form a twisted or coiled yarn.
  • the guest material is trapped within the helical corridors of the yarn.
  • micro-sized graphene oxide is dispersed in water, and deposited on a stack of forest-drawn CNT sheets. Thereafter, the resulting bilayer is twisted to make twisted or coiled graphene oxide/CNT yarns. This yarn is subsequently annealed at high temperature in vacuum to reduce the graphene oxide to graphene.
  • This incorporation of graphene into a coiled CNT yarn provides a coiled yarn that is highly elastic, able to be reversibly stretched by over 50% even when the spring index is as small as 0.75. Using 1 Hz sinusoidal stretch to 100% strain, such yarns were able to provide over 240 mV peak-to-peak change in open circuit voltage, over 120 W/kg of peak power, and over 40 J/kg of electrical energy per cycle.
  • graphene was deposited into a previously-twisted CNT yarn from a dispersion of graphene oxide by electrochemical deposition and reduction. Deposition was performed by immersing the yarn in a 1 M LiClO 4 electrolyte containing around 2.5 mg/mL of dispersed graphene oxide, and applying a ⁇ 1.2 V potential relative to an Ag/AgCl reference electrode. The incorporation of graphene into the yarn resulted in a harvester capable of delivering over 280 mV of peak-to-peak change in open circuit voltage, a peak power of 330 W/kg, and an energy per cycle of over 75 J/kg during 1 Hz sinusoidal stretching.
  • Twistron harvesters need not comprise CNTs.
  • the capacitance changes used for twistron energy harvesting can result from the effect of twist on either host nanofibers or guest materials. It is necessary for either the host yarn or guest particles to provide an electrically conducting pathway for collecting harvested charge. Additionally, it is necessary to provide an ionically conducting material inside the yarn. These requirements can be met by conducting percolated materials that are incorporated into an electrically insulating or electrically conducting yarn that does not comprise CNTs.
  • Graphitized nanofibers which can be obtained by pyrolyzing electrospun polymers, like polyacrylonitrile, (Zussman 2005; Kim 2003) provide an attractive alternative material to carbon nanotubes for use in twistron yarns, since they can be spun to below 100 nm diameters and be modified by conventional surface treatment means to provide the electrochemical properties needed for a twistron harvester.
  • carbon nanofiber as the yarn component that directly provides the mechanically-induced capacitance changes used for harvesting mechanical energy as electrical energy
  • these yarns can act as the host for a capacitance changing guest.
  • Useful examples of such guest capacitance-changing materials are carbon nanotubes, carbon nanohorns, graphene, fullerenes, activated carbon, carbon black, and combinations thereof.

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